EP0963428A1 - Antiwear agents for lubricating compositions - Google Patents
Antiwear agents for lubricating compositionsInfo
- Publication number
- EP0963428A1 EP0963428A1 EP98964505A EP98964505A EP0963428A1 EP 0963428 A1 EP0963428 A1 EP 0963428A1 EP 98964505 A EP98964505 A EP 98964505A EP 98964505 A EP98964505 A EP 98964505A EP 0963428 A1 EP0963428 A1 EP 0963428A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- sulfur
- oil
- hydrocarbyl radical
- oils
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 230000001050 lubricating effect Effects 0.000 title claims description 12
- -1 acyclic borate thioesters Chemical class 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 150000002148 esters Chemical class 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 125000004122 cyclic group Chemical class 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims description 76
- 239000000654 additive Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 7
- KXPXKNBDCUOENF-UHFFFAOYSA-N 2-(Octylthio)ethanol Chemical group CCCCCCCCSCCO KXPXKNBDCUOENF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 claims description 3
- ZPIRWAHWDCHWLM-UHFFFAOYSA-N 2-dodecylsulfanylethanol Chemical compound CCCCCCCCCCCCSCCO ZPIRWAHWDCHWLM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007866 anti-wear additive Substances 0.000 abstract description 17
- 150000001260 acyclic compounds Chemical class 0.000 abstract description 2
- 150000001923 cyclic compounds Chemical class 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 69
- 239000003963 antioxidant agent Substances 0.000 description 13
- 239000010687 lubricating oil Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 235000006708 antioxidants Nutrition 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 125000002015 acyclic group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229920002367 Polyisobutene Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- KVMLLMYIZCJDCT-UHFFFAOYSA-N 4-hydroxy-1,3,2,4-dioxathiaboretane Chemical compound S1OB(O1)O KVMLLMYIZCJDCT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000010689 synthetic lubricating oil Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RDAGYWUMBWNXIC-UHFFFAOYSA-N 1,2-bis(2-ethylhexyl)benzene Chemical compound CCCCC(CC)CC1=CC=CC=C1CC(CC)CCCC RDAGYWUMBWNXIC-UHFFFAOYSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical class CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- 150000004869 1,3,4-thiadiazoles Chemical class 0.000 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VXXDXJJJTYQHPX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)CO.OCC(CO)(CO)CO VXXDXJJJTYQHPX-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- NDLNTMNRNCENRZ-UHFFFAOYSA-N 2-[2-hydroxyethyl(octadecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCCCCN(CCO)CCO NDLNTMNRNCENRZ-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CLPFFLWZZBQMAO-UHFFFAOYSA-N 4-(5,6,7,8-tetrahydroimidazo[1,5-a]pyridin-5-yl)benzonitrile Chemical compound C1=CC(C#N)=CC=C1C1N2C=NC=C2CCC1 CLPFFLWZZBQMAO-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- YYPYFBVEXBVLBS-UHFFFAOYSA-N [B].[S] Chemical compound [B].[S] YYPYFBVEXBVLBS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
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- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2215/064—Di- and triaryl amines
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- C10M2215/22—Heterocyclic nitrogen compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2215/221—Six-membered rings containing nitrogen and carbon only
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C10M2223/042—Metal salts thereof
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
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- C10M2229/051—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
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- C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- the invention relates generally to compounds useful as antiwear additives for oleaginous compositions.
- the present invention relates to acyclic borate thioester and cyclic metaborate thioalkylester compounds suitable for use as antiwear additives for lubricating and power transmitting oils or fluids.
- Boron-containing compounds particularly borate esters, are known to act as antiwear agents when added to lubricating oils.
- EP-A-0216909 discloses antiwear agents that are esters of metaboric acid, and have the following formula:
- each R is independently hydrogen or a hydrocarbyl group containing from 1 to 18 carbon atoms and each R is independently an alkylene group containing from 2 to 4 carbon atoms.
- sulfur-containing compounds act as anti- oxidants in lubricating compositions and can further enhance the effect of boron-based antiwear agents.
- European Patent Specification discloses the use of the defined metaboric acid ester in combination with an oil-soluble sulfurized organic compound in relative amounts sufficient to provide a weight ratio of sulfur to boron of from 0.5:1 to 20:1.
- Antiwear agents providing both boron and sulfur are disclosed in, for example, US-A-3303130, which describes an organo thioalkyl borate antiwear agent of the general formula:
- R is selected from the group consisting of hydrogen, alkyl, aryl. alkaryl. aralkyl and cycloalkyl radicals containing 1 to 16 carbon atoms and n is an integer of 2 to 16, inclusive.
- R is selected from the group consisting of hydrogen, alkyl, aryl. alkaryl. aralkyl and cycloalkyl radicals containing 1 to 16 carbon atoms and n is an integer of 2 to 16, inclusive.
- These compounds are formed by reacting a thioalcohol with boric acid in a molar ratio of at least 3:1, and provide an antiwear additive having a weight ratio of sulfur to boron of 3.33: 1.
- Similar compounds formed by reacting an alcohol, a hydroxysulfide and a boron compound, and the use thereof as a friction reducer in lubricating oil compositions are disclosed in US-A- 4492640.
- the present invention provides an improved antiwear additive for lubricating oils which comprises a single compound that provides a relatively high weight ratio of boron to sulfur, while simultaneously providing antioxidant and friction modifier properties.
- the present invention provides a sulfur-containing boroester compound comprising: an acyclic thioalkyl borate ester having the general formula (I):
- R 1 represents a hydrocarbyl radical having from 4 to 12 carbon atoms
- R independently represent -(OR 4 ) n SR or -(OR ) n SR OH;
- R4 represents a hydrocarbyl radical having from 1 to 6 carbon atoms;
- n is an integer of from between about 1 to 4; and 1 and m are independently 0, 1 or 2; or a thioalkyl-substituted cyclic metaborate ester having the general formula
- n, R 1 and R 4 are defined as in formula (I); or a mixture of the acyclic thioalkyl borate ester of formula (I) and the thioalkyl-substituted cyclic metaborate ester of formula (II).
- the invention provides an oleaginous composition comprising, or made by admixing, a major amount of an oil of lubricating viscosity or of a power transmitting oil and a minor amount of a sulfur-containing boroester as defined in the first aspect of the invention.
- the invention provides a method of making an oleaginous composition comprising blending a major amount of an oil of lubricating viscosity or of a power transmitting oil and a minor amount of a sulfur-containing boroester as defined in the first aspect of the invention.
- the invention provides an additive concentrate comprising a sulfur- containing boroester compound as defined in the first aspect of the invention and an oleaginous carrier therefor.
- the invention provides a process for forming a sulfur-containing compound, such as a sulfur-containing boroester compound as defined in the first aspect of the invention, which comprises reacting at least an equivalent molar amount of boric acid with an alkoxyalkyl sulfide.
- the invention provides the use of a sulfur-containing boroeaster compound for improving the antiwear properties of lubricating or power transmitting oils or fluids.
- R 1 represents a hydrocarbyl radical having from between 6 to 9 carbon atoms
- R 4 represents a hydrocarbyl radical having from between 2 to 4 carbon atoms
- m and n are all 1. More preferably R represents a hydrocarbyl radical having 6 carbon atoms; and R represents a hydrocarbyl radical having 2 carbon atoms.
- acyclic borate thioester and cyclic metaborate thioester antiwear additives of the present invention may be the product of a condensation reaction of an alkoxyalkyl sulfide and boric acid in a molar ratio of at least about 1 :1.
- Suitable alkoxyalkyl sulfides are compounds of formula (III):
- Preferable compounds of formula III include hydroxyethyldodecyl sulfide, l-hydroxy-2-methyl-3-thio-decane and hydroxyethyloctyl sulfide (HEOS).
- HEOS hydroxyethyloctyl sulfide
- the alkoxyalkyl sulfide can comprise a single compound or a mixture thereof.
- the alkoxyalkyl sulfide When reacted with boric acid, the alkoxyalkyl sulfide may form a reaction product that can include both the acyclic compound of formula I and the cyclic compound of formula II.
- the reaction strongly favours formation of the cyclic metaborate thioester and the reaction product may, in fact, contain only insignificant amounts, or essentially no, acyclic borate thioester.
- the boric acid and hydroxalkyl sulfide may be reacted in a molar ratio of about 1 : 1 or can be reacted in the presence of a slight molar excess of alkoxyalkyl sulfide (no greater than about 2: 1).
- the reaction may be conducted at a temperature of from 0 to 150, preferably from 60 to 120,°C and at a pressure from -100 to O,preferably from -70 to -30, kPa.
- the boric acid and hydroxalkyl sulfide may be reacted either neat or in an inert or non-participating polar solvent.
- HEOS hydroxyethyloctyl sulfide
- boric acid reactants as examples, the reaction is believed to proceed as follows:
- Lubricating oils and power transmitting oils to which the antiwear additives of the invention can be advantageously added are derived from natural oils, synthetic oils or mixtures of natural oils and synthetic oils.
- Suitable oils include base stocks obtained by isomerization of synthetic wax and slack wax, as well as base stocks produced by hydrocracking the aromatic and polar components of the crude.
- Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene, isobutylene copolymers, chlorinated polyactenes, poly(l- hexenes), poly(l-octenes), poly(l-decenes), and mixtures thereof); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzene); polyphenyls (e.g...
- Synthetic oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof where the terminal hydroxyl groups have been modified by (for example) esterification or etherification.
- This class of synthetic oils can be exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; as well as the alkyl or aryl ethers of these polyoxyalkylene polymers (e.g., methyl- polyisopropylene glycol ether having a number average molecular weight of 1000 and diphenyl ether of polypropylene glycol having a number average molecular weight of 1000 to 1500), and mono- and poly-carboxylic esters thereof (e.g., acetic acid esters, mixed C 3 to C 8 fatty acid esters and C )2 oxo diester of tetraethylene glycol).
- Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids and alkenylmalonic acids) with an alcohol (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethers and propylene glycol).
- dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer,
- esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl isophthalate, didecyl phthalate, dielcosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid.
- Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane pentaerythritol, dipentaerythritol and tripentaerythritol.
- Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic oils. These oils include tetra-ethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2- ethylhexyl) silicate, tetra-(p-tertbutylphenyl) silicate, hexa-(4-methyl-2-pentoxy)- disiloxane, poly(methyl) siloxanes and poly(methylphenyl) siloxanes.
- oils include tetra-ethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2- ethylhexyl) silicate,
- Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decylphosphonic acid), polymeric tetra-hydrofurans and poly- ⁇ -olefins.
- Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale.
- Mineral oils to which the antiwear additives of the invention can be added include all common mineral oil base stocks. This includes oils that are naphthenic or paraffinic in chemical structure.
- the oils may be refined by conventional methodology using acid, alkali, and clay or other agents such as aluminum chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents such as phenol, sulfur dioxide, furfural or dichlordiethyl ether. They may also be hydrotreated or hydrorefined, dewaxed by chilling or by catalytic processing, or hydrocracked.
- the mineral oil may also be produced from natural crude sources " or be composed of isomerized wax materials or residues of other refined processes.
- the lubricating or power transmitting oils may be derived from unrefined oils, highly refined oils, re-refined oils or mixtures thereof.
- Unrefined oils are obtained directly from natural sources or synthetic sources (e.g., shale or tar sands bitumen) without further purification or treatment.
- unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is used without further treatment.
- Refined oils are similar to unrefined oils except that the refined oils have been treated in one or more purification steps to improve one or more properties.
- Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration and percolation, all of which are known to those of ordinary skill in the art.
- Re-refined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and are often additionally processed by techniques for removal of spent additives and oil breakdown products.
- the compounds of the invention can be incorporated into lubricating oils and power transmitting oils as antiwear additives in an amount from 0.001 to 5, preferably from 0.001 to 1.5, most preferably from 0.2 to 1.0, mass %.
- the oleaginous materials may be formulated to contain other additives such as viscosity modifiers, auxiliary antioxidants, friction modifiers, dispersants, antifoaming agents, auxiliary antiwear agents, pour point depressants, detergents, and rust inhibitors.
- compositions essential as well as optimal and customary, may react under the conditions of formulation, storage, or use, and that the invention also provides the product obtainable or obtained as a result of any such reaction.
- compositions containing the above additives are typically blended into base oils in amounts sufficient to provide their normal attendant function.
- amounts in which these additives are conventionally blended to lubricating oils are as follows:
- the additives can be incorporated into the lubricating oil in any convenient manner. Thus, they can be added directly to the oil by dispersing or dissolving same in the oil. Such blending can be performed at room temperature or at elevated temperatures. Alternatively, the additives may be first formed into concentrates comprising the additives in an oleaginous carrier therefor, which are subsequently blended with the oil. The final formulations may typically contain from 2 to 20 mass % of additives.
- Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed ester/amides of hydrocarbyl-substituted succinic acid, hydroxyesters of hydrocarbyl- substituted succinic acid, amides of aromatic acids and Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines. Mixtures of such dispersants can also be employed.
- the dispersants may optionally be post-treated with conventional reagents known in the art (see, e.g., U -S- Patent Nos. 3,254,025; 3,505,677; and 4,857,214).
- the preferred dispersant for use in combination with the sulfur boron antiwear additives of the present invention are alkenyl succinimides. These acyclic hydrocarbyl-substituted succinimides are formed with various amines, polyamines and amine derivatives, and are well known to those of ordinary skill in the art.
- An example of a particularly suitable dispersant is the polyisobutenyl succinimide reaction product of polyisobutylene succinic anhydride, wherein the polyisobutene moiety preferably has a number average molecular weight in the range from 500 to 5000, preferably from 800 to 2500.
- alkenyl succinimides that have been treated with an inorganic acid of phosphorus (or an anhydride thereof) and a boronating agent are also suitable for use in combination with the compounds of the invention and are more compatible with elastomeric seals made from such substances as fluoroelastomers and silicon-containing elastomers.
- Suitable antioxidants for use in combination with the additives of the present invention include amine-type and phenolic antioxidants.
- amine-type antioxidants include phenyl alpha naphthylamine, phenyl beta naphthylamine and bis- alkylated diphenyl amines (e.g., p,p'-bis(alkylphenyl)- amines wherein the alkyl groups each contain from 8 to 12 carbon atoms).
- Phenolic antioxidants include sterically hindered phenols (e.g., 2,6-di-tertbutylphenol, 4-methyl-2,6-di-tert-butylphenol) and bis-phenols (e.g., 4,4"-methylenebis(2,6-di-tert-butylphenol).
- Phosphorus compounds, such as ZDDP, or phosphates are also commonly added to automatic transmission fluids (ATF) and passenger car motor oils (PCMO) as antioxidants.
- ATF automatic transmission fluids
- PCMO passenger car motor oils
- the compounds of the present invention provide antioxidant credits to lubricating compositions, allowing for the formulation of lubricating compositions with a reduced amount, or no amount, of dedicated antioxidant additive.
- Suitable friction modifiers are molecules having a polar head group and an oleophilic tail group.
- the polar head groups cause the molecule to be adsorbed onto the friction surface.
- These groups can be, but are not limited to, amines, mono- and diethoxylated amines, carboxylic acids, amides, imides, alcohols, phenols, thiols, sulfonic acids, phosphates, phosphates, esters and combinations thereof.
- the oleophilic groups are typically alkyl groups, normally linear alkyl groups. These alkyl groups range in carbon number from between C 8 to C 30 , preferably from C ]2 to C 20 .
- friction modifiers suitable for use with the antiwear additives of the invention include oleamide; tallow amine; diethoxylated tallow amine; N,N-bis(2- hydroxyethyl)-octadecyl amine; N.N-bis(2-hydroxyethyl)- stearyloxypropylamine; oleic acid; N.N-hydroxyethyl.N-(N',N'-bis(2-hydroxyethyl)ethylamine)-stearylamine; and the diamide produced from isostearic acid and tetraethylene pentamine.
- Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters.
- Oil soluble viscosity modifying polymers generally have weight average molecular weights from 10,000 to 1 ,000,000, preferably from 20,000 to 500,000, as determined by gel permeation chromatography or light scattering methods.
- suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acid and vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene and isoprene/butadiene, as well as partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
- Lubricating oils and power transmission oils incorporating the antiwear additives of the invention may also contain rust inhibitors such as nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols and anionic alkyl sulfonic acids, as well as corrosion inhibitors, such as thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof; derivatives of 1,3,4-thiadiazoles; and thio and polythio sulfenamides of thiadiazoles.
- rust inhibitors such as nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols and anionic alkyl sulfonic acids, as well as corrosion inhibitors, such as thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof; derivatives of 1,3,4-thiadiazoles; and thio and polythio sulfenamides of thi
- Such oils may also contain an antifoamant, including polyacrylate-type antifoamants, polysiloxane-type antifoamants and fluorosilicone-type antifoamants, and detergents, such as overbased and neutral calcium sulfonate, calcium phenate, magnesium sulfonate and magnesium phenate.
- an antifoamant including polyacrylate-type antifoamants, polysiloxane-type antifoamants and fluorosilicone-type antifoamants, and detergents, such as overbased and neutral calcium sulfonate, calcium phenate, magnesium sulfonate and magnesium phenate.
- the product was characterized by a combination of analytical techniques. HPLC separation analysis showed that one primary species was formed. 13 C NMR Spectroscopy indicated that the material had a characteristic sharp single resonance associated with a borated alkoxy methylene carbon at 62.8(1C) ppm relative toTMS. B NMR Spectroscopy showed only one boro-oxygen ester signal at -3 ppm relative to H 3 BO 3 . The simplicity of the carbon and boron NMR spectral result was indicative of a highly symmetric meta-boroester structure.
- Characteristic carbon signals associated with the incorporation of hydroxyethyloctyl sulfide were found at 33(1C), 31.8(1C), 31.2(1C), 29.6(1C), 28.8(1C), 28.6(1C), 22.4(1C) and 13.6(1C).
- Additive Packages A to G were formulated as shown below and added to a viscosity modified base oil at a 7 mass % treat rate to form formulated oils.
- the formulated oils were then subjected to LMOT testing (described below) to determine antioxidancy improvements, and FZG testing (Four Square Gear Test, ASTMD-5182) to determine antiwear activity.
- the Laboratory Multiple Oxidation Test is used to measure the ability of lubricant compositions to resist heat and air oxidation.
- 50cc of a test lubricant 2.2g of iron filings, and 0.5g of a 1% copper solution (Nuodex® Copper 82 copper naphthenate in mineral spirits made into a 1% solution by dissolution of Nuodex 8% copper in I00NLP oil (Exxon Chemical)).
- a temperature of 150°C + 2°C air is passed through the sample (25cc +_ 2cc/min.).
- One drop per day of the sample lubricant is placed on a blotter until sludge appears.
- the results of the LMOT are presented in terms of days until sludge is observed (days to failure).
- Adpack D containing 0.46 mass % HEOS metaborate ester
- Adpack F and G additional HEOS metaborate ester
- the results of the LMOT testing display the ability of the HEOS metaborate ester to simultaneously function as an antioxidant.
- Adpacks A to D containing 0.46 HEOS metaborate ester
- Adpack F or G which contained 0.92 mass % of the HEOS metaborate ester, provided a four day increase in the LMOT result compared with the composition formulated with Adpack E.
- Lubricating oils are typically required to meet industry standards for oxidation performance. Antioxidants are normally added into these oils to prevent the oxidative degradation that normally occurs during usage. In PCMO and ATF lubricants, phosphorus compounds, such as ZDDP or phosphates, are often used for this purpose. The following tests demonstrate that the antioxidant effect of the HEOS metaborate ester antiwear additive of the present invention is sufficiently high to allow the formulation of an oil without an additional ZDDP or phosphite antioxidant.
- friction reducers allow formulators to adjust the coefficient of friction to meet these needs.
- a combination of a HEOS metaborate ester and dispersant was found to provide excellent friction reducing characteristics.
- a reference oil fully formulated with dispersant (5.5 wt.%), antifoamant, detergent, phosphorus-based antiwear/antioxidant and demulsifier additives, but containing no friction reducer, was compared with the same oil further formulated with 2.1 1 wt.% HEOS metaborate ester and 7.69 wt.% dispersant (Adpack O) using a High Frequency Reciprocal Rig(HFRR) test.
- HFRR High Frequency Reciprocal Rig
- a metal ball is affixed to the end of the vibrator arm.
- a sample of a lubricating oil is pipetted into the bath, immersing the disc, and the vibrator arm is lowered so that the ball contacts the disc.
- the vibrator arm is then vibrated at a frequency of 20Hz, with a stroke of 1000 microns. After each five minute period the temperature of the oil sample is increased 20°C (6 steps from 40°C to 140°C).
- the disc is then removed from the platen, and the wear scar caused by contact with the ball is measured (diameters X and Y) using an optical microscope provided with a calibrated graticule.
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Abstract
Sulfur-containing boroester compounds useful as antiwear additives for oleaginous compositions including acyclic borate thioesters having general formula (I) wherein R1 represents a hydrocarbyl radical having between 4 to 12 carbon atoms, R?2 and R3¿ independently represent -(OR4)nSR1 and -(OR4)nSR1OH; R4 represents a hydrocarbyl radical having between 1 to 6 carbon atoms; n is an integer of from between 1 to 4; and 1 and m are independently 0, 1 or 2; or thioalkyl-substituted cyclic metaborate ester having general formula (II) wherein n, R?1 and R4¿, are defined as in formula (I); or a mixture of the acyclic compounds of formula (I) and the cyclic compounds of formula (II).
Description
ANTIWEAR AGENTS FOR LUBRICATING COMPOSITIONS
The invention relates generally to compounds useful as antiwear additives for oleaginous compositions. In particular, the present invention relates to acyclic borate thioester and cyclic metaborate thioalkylester compounds suitable for use as antiwear additives for lubricating and power transmitting oils or fluids.
Boron-containing compounds, particularly borate esters, are known to act as antiwear agents when added to lubricating oils. EP-A-0216909 discloses antiwear agents that are esters of metaboric acid, and have the following formula:
(OR')nOR
B
O O
RO(RO)n B ^ ^ B (OR')nOR
*O'
wherein each R is independently hydrogen or a hydrocarbyl group containing from 1 to 18 carbon atoms and each R is independently an alkylene group containing from 2 to 4 carbon atoms.
It is further well-known that sulfur-containing compounds act as anti- oxidants in lubricating compositions and can further enhance the effect of boron-based antiwear agents. The above-described European Patent Specification discloses the use of the defined metaboric acid ester in combination with an oil-soluble sulfurized organic compound in relative amounts sufficient to provide a weight ratio of sulfur to boron of from 0.5:1 to 20:1.
Antiwear agents providing both boron and sulfur are disclosed in, for example, US-A-3303130, which describes an organo thioalkyl borate antiwear agent of the general formula:
O(CH2)nSR
/ RS(CH2)nO-B
\ O(CH2)nSR
wherein R is selected from the group consisting of hydrogen, alkyl, aryl. alkaryl. aralkyl and cycloalkyl radicals containing 1 to 16 carbon atoms and n is an integer of 2 to 16, inclusive. These compounds are formed by reacting a thioalcohol with boric acid in a molar ratio of at least 3:1, and provide an antiwear additive having a weight ratio of sulfur to boron of 3.33: 1. Similar compounds formed by reacting an alcohol, a hydroxysulfide and a boron compound, and the use thereof as a friction reducer in lubricating oil compositions are disclosed in US-A- 4492640.
Because of increased demand for lubricating oil additives and fierce competition between manufacturers, there has been a continued need for improved antiwear additives. The present invention provides an improved antiwear additive for lubricating oils which comprises a single compound that provides a relatively high weight ratio of boron to sulfur, while simultaneously providing antioxidant and friction modifier properties.
In a first aspect, the present invention provides a sulfur-containing boroester compound comprising: an acyclic thioalkyl borate ester having the general formula (I):
(OB)mR2 R1S(R4O)n-B (I)
\
(OB)iRJ
wherein R 1 represents a hydrocarbyl radical having from 4 to 12 carbon atoms, R 2 and
R independently represent -(OR4)nSR or -(OR )nSR OH; R4 represents a hydrocarbyl radical having from 1 to 6 carbon atoms; n is an integer of from between about 1 to 4; and 1 and m are independently 0, 1 or 2; or a thioalkyl-substituted cyclic metaborate ester having the general formula
(II):
wherein n, R1 and R4, are defined as in formula (I); or a mixture of the acyclic thioalkyl borate ester of formula (I) and the thioalkyl-substituted cyclic metaborate ester of formula (II).
In a second aspect, the invention provides an oleaginous composition comprising, or made by admixing, a major amount of an oil of lubricating viscosity or of a power transmitting oil and a minor amount of a sulfur-containing boroester as defined in the first aspect of the invention.
In a third aspect, the invention provides a method of making an oleaginous composition comprising blending a major amount of an oil of lubricating viscosity or of a power transmitting oil and a minor amount of a sulfur-containing boroester as defined in the first aspect of the invention.
In a fourth aspect, the invention provides an additive concentrate comprising a sulfur- containing boroester compound as defined in the first aspect of the invention and an oleaginous carrier therefor.
In a fifth aspect, the invention provides a process for forming a sulfur-containing compound, such as a sulfur-containing boroester compound as defined in the first aspect of the invention, which comprises reacting at least an equivalent molar amount of boric acid with an alkoxyalkyl sulfide.
In a sixth aspect, the invention provides the use of a sulfur-containing boroeaster compound for improving the antiwear properties of lubricating or power transmitting oils or fluids.
The invention will now be discussed in more detail as follows.
In the sulfur-containing boroester compound of the invention, whether the acyclic or cyclic, it is preferred that R1 represents a hydrocarbyl radical having from between 6 to 9 carbon atoms; R4 represents a hydrocarbyl radical having from between 2 to 4 carbon atoms; and 1, m and n are all 1. More preferably R represents a hydrocarbyl radical having 6 carbon atoms; and R represents a hydrocarbyl radical having 2 carbon atoms.
The acyclic borate thioester and cyclic metaborate thioester antiwear additives of the present invention may be the product of a condensation reaction of an alkoxyalkyl sulfide and boric acid in a molar ratio of at least about 1 :1. Suitable
alkoxyalkyl sulfides are compounds of formula (III):
R!SR4OH (III) wherein R1 and R4 are defined as above. Preferable compounds of formula III include hydroxyethyldodecyl sulfide, l-hydroxy-2-methyl-3-thio-decane and hydroxyethyloctyl sulfide (HEOS). The alkoxyalkyl sulfide can comprise a single compound or a mixture thereof.
When reacted with boric acid, the alkoxyalkyl sulfide may form a reaction product that can include both the acyclic compound of formula I and the cyclic compound of formula II. The reaction strongly favours formation of the cyclic metaborate thioester and the reaction product may, in fact, contain only insignificant amounts, or essentially no, acyclic borate thioester. The boric acid and hydroxalkyl sulfide may be reacted in a molar ratio of about 1 : 1 or can be reacted in the presence of a slight molar excess of alkoxyalkyl sulfide (no greater than about 2: 1). The reaction may be conducted at a temperature of from 0 to 150, preferably from 60 to 120,°C and at a pressure from -100 to O,preferably from -70 to -30, kPa.
The boric acid and hydroxalkyl sulfide may be reacted either neat or in an inert or non-participating polar solvent. Using hydroxyethyloctyl sulfide (HEOS) and boric acid reactants as examples, the reaction is believed to proceed as follows:
Lubricating oils and power transmitting oils to which the antiwear additives of the invention can be advantageously added are derived from natural oils, synthetic oils or mixtures of natural oils and synthetic oils. Suitable oils include base stocks obtained by isomerization of synthetic wax and slack wax, as well as base stocks produced by hydrocracking the aromatic and polar components of the crude.
Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene, isobutylene copolymers, chlorinated polyactenes, poly(l- hexenes), poly(l-octenes), poly(l-decenes), and mixtures thereof); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzene);
polyphenyls (e.g.. biphenyls, terphenyls, alkylated polyphenyls); and alkylated diphenyl ethers, alkylated diphenyl sulfides. as well as derivatives, analogues and homologues thereof.
Synthetic oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof where the terminal hydroxyl groups have been modified by (for example) esterification or etherification. This class of synthetic oils can be exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; as well as the alkyl or aryl ethers of these polyoxyalkylene polymers (e.g., methyl- polyisopropylene glycol ether having a number average molecular weight of 1000 and diphenyl ether of polypropylene glycol having a number average molecular weight of 1000 to 1500), and mono- and poly-carboxylic esters thereof (e.g., acetic acid esters, mixed C3 to C8 fatty acid esters and C)2 oxo diester of tetraethylene glycol).
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids and alkenylmalonic acids) with an alcohol (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethers and propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl isophthalate, didecyl phthalate, dielcosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid.
Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane pentaerythritol, dipentaerythritol and tripentaerythritol.
Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic oils. These oils include tetra-ethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2- ethylhexyl) silicate, tetra-(p-tertbutylphenyl) silicate, hexa-(4-methyl-2-pentoxy)- disiloxane, poly(methyl) siloxanes and poly(methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decylphosphonic acid), polymeric tetra-hydrofurans and poly-α-olefins.
Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale. Mineral oils to which the antiwear additives of the invention can be added include all common mineral oil base stocks. This includes oils that are naphthenic or paraffinic in chemical structure. The oils may be refined by conventional methodology using acid, alkali, and clay or other agents such as aluminum chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents such as phenol, sulfur dioxide, furfural or dichlordiethyl ether. They may also be hydrotreated or hydrorefined, dewaxed by chilling or by catalytic processing, or hydrocracked. The mineral oil may also be produced from natural crude sources "or be composed of isomerized wax materials or residues of other refined processes.
The lubricating or power transmitting oils may be derived from unrefined oils, highly refined oils, re-refined oils or mixtures thereof. Unrefined oils are obtained directly from natural sources or synthetic sources (e.g., shale or tar sands bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is used without further treatment. Refined oils are similar to unrefined oils except that the refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration and percolation, all of which are known to those of ordinary skill in the art. Re-refined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and are often additionally processed by techniques for removal of spent additives and oil breakdown products.
The compounds of the invention can be incorporated into lubricating oils and power transmitting oils as antiwear additives in an amount from 0.001 to 5, preferably from 0.001 to 1.5, most preferably from 0.2 to 1.0, mass %. The oleaginous materials may be formulated to contain other additives such as viscosity modifiers, auxiliary antioxidants, friction modifiers, dispersants, antifoaming agents, auxiliary antiwear agents, pour point depressants, detergents, and rust inhibitors.
It will be understood that the various components of the composition, essential as well as optimal and customary, may react under the conditions of formulation, storage, or use,
and that the invention also provides the product obtainable or obtained as a result of any such reaction.
Compositions containing the above additives are typically blended into base oils in amounts sufficient to provide their normal attendant function. Representative examples of amounts in which these additives are conventionally blended to lubricating oils are as follows:
Additive wt.% (broad)* Wt.%(preferred)
Viscosity Modifier .01-12 .01-4
Corrosion Inhibitor .01-5 .01-1.5
Oxidation Inhibitor .01-5 .01-1.5
Dispersant .1-20 .1-8
Pour Point Depressant .01-5 .01-1.5
Anti-Foaming Agents .001-3 .001-0.15
Anti-Wear Agents .001-5 .001-1.5
Friction Modifiers .01-5 .01-3
Detergents/Rust inhibitors .01-10 .01-3
Base Oil Balance Balance
* active ingredient
The additives can be incorporated into the lubricating oil in any convenient manner. Thus, they can be added directly to the oil by dispersing or dissolving same in the oil. Such blending can be performed at room temperature or at elevated temperatures. Alternatively, the additives may be first formed into concentrates comprising the additives in an oleaginous carrier therefor, which are subsequently blended with the oil. The final formulations may typically contain from 2 to 20 mass % of additives.
Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed ester/amides of hydrocarbyl-substituted succinic acid, hydroxyesters of hydrocarbyl- substituted succinic acid, amides of aromatic acids and Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines. Mixtures of such dispersants can also be employed. The dispersants may optionally be post-treated with conventional reagents known in the art (see, e.g., U -S- Patent Nos. 3,254,025; 3,505,677; and 4,857,214).
The preferred dispersant for use in combination with the sulfur boron
antiwear additives of the present invention are alkenyl succinimides. These acyclic hydrocarbyl-substituted succinimides are formed with various amines, polyamines and amine derivatives, and are well known to those of ordinary skill in the art. An example of a particularly suitable dispersant is the polyisobutenyl succinimide reaction product of polyisobutylene succinic anhydride, wherein the polyisobutene moiety preferably has a number average molecular weight in the range from 500 to 5000, preferably from 800 to 2500. and an alkylene polyamine such as triethylene tetramine or tetraethylene pentamine or mixtures of polyamines containing 3 to 12 nitrogen atoms per molecule, known in the art as PAM. The use of alkenyl succinimides that have been treated with an inorganic acid of phosphorus (or an anhydride thereof) and a boronating agent are also suitable for use in combination with the compounds of the invention and are more compatible with elastomeric seals made from such substances as fluoroelastomers and silicon-containing elastomers.
Suitable antioxidants for use in combination with the additives of the present invention include amine-type and phenolic antioxidants. Examples of amine-type antioxidants include phenyl alpha naphthylamine, phenyl beta naphthylamine and bis- alkylated diphenyl amines (e.g., p,p'-bis(alkylphenyl)- amines wherein the alkyl groups each contain from 8 to 12 carbon atoms). Phenolic antioxidants include sterically hindered phenols (e.g., 2,6-di-tertbutylphenol, 4-methyl-2,6-di-tert-butylphenol) and bis-phenols (e.g., 4,4"-methylenebis(2,6-di-tert-butylphenol). Phosphorus compounds, such as ZDDP, or phosphates are also commonly added to automatic transmission fluids (ATF) and passenger car motor oils (PCMO) as antioxidants. In addition to providing antiwear properties, the compounds of the present invention provide antioxidant credits to lubricating compositions, allowing for the formulation of lubricating compositions with a reduced amount, or no amount, of dedicated antioxidant additive.
Suitable friction modifiers are molecules having a polar head group and an oleophilic tail group. The polar head groups cause the molecule to be adsorbed onto the friction surface. These groups can be, but are not limited to, amines, mono- and diethoxylated amines, carboxylic acids, amides, imides, alcohols, phenols, thiols, sulfonic acids, phosphates, phosphates, esters and combinations thereof. The oleophilic groups are typically alkyl groups, normally linear alkyl groups. These alkyl groups range in carbon number from between C8 to C30, preferably from C]2 to C20. They may be saturated or unsaturated, and may contain hetero atoms such as nitrogen or sulfur providing that the hetero atoms do not adversely affect the ability of the molecule to function as a friction modifier.
Examples of friction modifiers suitable for use with the antiwear additives of the invention include oleamide; tallow amine; diethoxylated tallow amine; N,N-bis(2- hydroxyethyl)-octadecyl amine; N.N-bis(2-hydroxyethyl)- stearyloxypropylamine; oleic acid; N.N-hydroxyethyl.N-(N',N'-bis(2-hydroxyethyl)ethylamine)-stearylamine; and the diamide produced from isostearic acid and tetraethylene pentamine.
Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters. Oil soluble viscosity modifying polymers generally have weight average molecular weights from 10,000 to 1 ,000,000, preferably from 20,000 to 500,000, as determined by gel permeation chromatography or light scattering methods.
Representative examples of suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acid and vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene and isoprene/butadiene, as well as partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
Lubricating oils and power transmission oils incorporating the antiwear additives of the invention may also contain rust inhibitors such as nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols and anionic alkyl sulfonic acids, as well as corrosion inhibitors, such as thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof; derivatives of 1,3,4-thiadiazoles; and thio and polythio sulfenamides of thiadiazoles. Such oils may also contain an antifoamant, including polyacrylate-type antifoamants, polysiloxane-type antifoamants and fluorosilicone-type antifoamants, and detergents, such as overbased and neutral calcium sulfonate, calcium phenate, magnesium sulfonate and magnesium phenate.
The invention will now be illustrated by the following examples.
EXAMPLE 1 (SYNTHESIS)
In a 5 liter, three neck flask, 2280 grams of hydroxyethyloctyl sulfide (12 mol) and 744 grams of boric acid powder (12 mol) were combined. The flask was equipped with a stirrer, a thermometer and a condenser connected to vacuum. The flask was heated to 110 °C, and pressure within the flask reduced to -7OkPa. After a few minutes water began to
evolve. The temperature in the flask was allowed to fall to 100°C at which point heating was terminated and the exothermic reaction proceeded unassisted until 2 molar equivalents of water evolved and were collected. Heat was then applied until one additional molar equivalent of water evolved and was collected.
The product was characterized by a combination of analytical techniques. HPLC separation analysis showed that one primary species was formed. 13 C NMR Spectroscopy indicated that the material had a characteristic sharp single resonance associated with a borated alkoxy methylene carbon at 62.8(1C) ppm relative toTMS. B NMR Spectroscopy showed only one boro-oxygen ester signal at -3 ppm relative to H3BO3. The simplicity of the carbon and boron NMR spectral result was indicative of a highly symmetric meta-boroester structure. Characteristic carbon signals associated with the incorporation of hydroxyethyloctyl sulfide were found at 33(1C), 31.8(1C), 31.2(1C), 29.6(1C), 28.8(1C), 28.6(1C), 22.4(1C) and 13.6(1C).
EXAMPLE 2
To demonstrate the ability of the compounds of the present invention to provide antiwear and antioxidant activity in lubricating oils, Additive Packages (Adpacks) A to G were formulated as shown below and added to a viscosity modified base oil at a 7 mass % treat rate to form formulated oils. The formulated oils were then subjected to LMOT testing (described below) to determine antioxidancy improvements, and FZG testing (Four Square Gear Test, ASTMD-5182) to determine antiwear activity.
Each Adpack (A to G) contained:
0.45% diphenylamine (antioxidant);
0.15% friction modifiers;
0.001% fluorinated silicone antifoamant;
3.5%) of a borated PIBSA-PAM (dispersant); and a base stock oil.
They differed in respect of the molecular weight of the PIB in the dispersant, the presence and amount of HEOS-metaborate ester of Example 1, the presence or otherwise of 0.50% tolyl triazole (corrosion inhibitor) and the amount of base stock oil, as shown in the table below.
represents presence and - represent absence All percentages and amounts are mass %
In the Adpacks, all percentages and amounts represent mass %.
The Laboratory Multiple Oxidation Test (LMOT) is used to measure the ability of lubricant compositions to resist heat and air oxidation. In the LMOT, 50cc of a test lubricant, 2.2g of iron filings, and 0.5g of a 1% copper solution (Nuodex® Copper 82 copper naphthenate in mineral spirits made into a 1% solution by dissolution of Nuodex 8% copper in I00NLP oil (Exxon Chemical)). At a temperature of 150°C + 2°C, air is passed through the sample (25cc +_ 2cc/min.). One drop per day of the sample lubricant is placed on a blotter until sludge appears. The results of the LMOT are presented in terms of days until sludge is observed (days to failure).
Table 1 below summarises the results.
TABLE 1
B D
Viscosity 8.2 8.2 8.8 8.9 8.0 8.6 10 at 100°C (mmV)
LMOT 8.5 9 1 1 10 7 1 1 1 1 at 320°F (160°C)
(days to failure)
FZG — — — 10 8 11 12
(failure stage)
As shown by the data of Table 1, the addition of adpack D, containing 0.46 mass % HEOS metaborate ester, to the base stock oil improved the FZG by two load stages compared with an oil formulated without the borate ester (Adpack E). The use of additional HEOS metaborate ester (Adpacks F and G) led to further improvement in antiwear properties. The results of the LMOT testing display the ability of the HEOS metaborate ester to simultaneously function as an antioxidant. Specifically, the data regarding Adpacks A to D, containing 0.46 HEOS metaborate ester, demonstrate an increased LMOT of 1.5 to 3 days compared with the oil formulated without the additive of the invention (Adpack E). The addition of Adpack F or G, which contained 0.92 mass % of the HEOS metaborate ester, provided a four day increase in the LMOT result compared with the composition formulated with Adpack E.
EXAMPLE 3
To demonstrate the results achieved when the additives of the invention are co- formulated with commonly used phosphorus-based additives, three oil compositions were formulated to contain 0.31 mass % HEOS metaborate ester and either 0.30 mass % triphenylphosphate (TPP) (Adpack H); 0.16 mass % of mixed phosphites (Adpack I); or 0.19 mass % dibutyl phosphite (DBP) (Adpack
J). The three formulated oils were subjected to FZG and LMOT testing. The results are shown below:
TABLE 2
H I J
Viscosity 8.03 7.99 7.99
At 100°C (mm2s"1)
LMOT 10.5 9 10.5
At 320°F (160°C) (days to failure)
FZG 9 10 12
(failure stage)
The data of Table 2 demonstrate that an adpack containing HEOS metaborate ester (0.31 mass %), co-formulated with phosphorus-based friction modifiers, simultaneously provide antiwear and antioxidant properties in formulated oils.
EXAMPLE 4
The antiwear properties of HEOS metaborate (0.31 wt.%)-dispersant combinations (PIBSA PAM (950 Mw polyisobutylene)) (3.5 wt.%), in which the HEOS-metaborate ester in an automatic transmission fluid (K) were compared with a fully formulated reference ATF (L) (containing no phosphorus-based, or other antiwear additives) in the industry standard Ford MERCON Vickers Pump Test (Ford Motor Company, MERCON Automatic Transmission Fluid Specification for Service, March 5, 1987). The strong antiwear performance of the borate ester-dispersant combination, shown below in Table 3, was surprising given that the ATF contained no other antiwear additives. The data of Table 4 compare the measured Vickers Pump wear for the additized oil with the industry standards.
TABLE 3
Additive Combination FZG Failing Load Stage
K 13 L 8
TABLE 4
ATF Fluid Wear Result GM Dextron 111* Pass/Fail Limit
12 mg Total Wear 15 mg maximum Total Wear
* Hydra-matic Division, General Motors Corp.
EXAMPLE 5
To demonstrate the antiwear performance of the HEOS metaborate ester and dispersant combination in passenger car motor oils (PCMO), a PCMO containing 3.5 wt.% of a standard PIBSA-PAM dispersant (M) was compared with a PCMO containing the same dispersant and 0.28 wt.% HEOS-metaborate ester (N). Corrosive wear with the two samples was compared using the industry standard L38 Wear Test (ASTM D-5119), the results being provided below in Table 5. As the data of Table 5 demonstrate, the addition of only 0.28 wt.% of the antiwear additive of the invention provided an approximately 50% improvement in the antiwear results.
TABLE 5
Additive L38 Wear Results (mg)
M 56.7
N 25.8
EXAMPLE 6
Lubricating oils are typically required to meet industry standards for oxidation performance. Antioxidants are normally added into these oils to prevent the
oxidative degradation that normally occurs during usage. In PCMO and ATF lubricants, phosphorus compounds, such as ZDDP or phosphates, are often used for this purpose. The following tests demonstrate that the antioxidant effect of the HEOS metaborate ester antiwear additive of the present invention is sufficiently high to allow the formulation of an oil without an additional ZDDP or phosphite antioxidant.
An ATF-containing Adpack N (described in Example 5) was subjected to a Ford MERCON Aluminum Beaker Oxidation Test (ABOT) (Ford MERCON method BJ110-4). The results achieved are compared with the industry standard limits in Table 6
TABLE 6
ABOT Result with Adpack N Industry Limit
Δ total acid no. (TAN) 1.28 <4.0
% viscosity increase @ 250hrs. 8.89 <40%
Diff IR @ 250hrs. 22.2% <40%
% pentane insol @ 250hrs. 0.53 <1.0
Cu Strip @ 300hrs. 3b 3b max
EXAMPLE 7
The frictional properties of lubricating oils play a significant role towards improving fuel economy in automobiles. Use of friction reducers allows formulators to adjust the coefficient of friction to meet these needs. A combination of a HEOS metaborate ester and dispersant was found to provide excellent friction reducing characteristics. To demonstrate these friction-reducing effects, a reference oil fully formulated with dispersant (5.5 wt.%), antifoamant, detergent, phosphorus-based antiwear/antioxidant and demulsifier additives, but containing no friction reducer, was compared with the same oil further formulated with 2.1 1 wt.% HEOS metaborate ester and 7.69 wt.% dispersant (Adpack O) using a High Frequency Reciprocal Rig(HFRR) test.
In the HFRR test, a metal disc is affixed to a platen within a bath. Opposite the platen, there is provided a vibrator arm to which a mass of 400g is attached. A metal ball is affixed to the end of the vibrator arm. A sample of a lubricating oil is pipetted into the bath, immersing the disc, and the vibrator arm is lowered so that the ball contacts the disc. The vibrator arm is then vibrated at a frequency of 20Hz, with a stroke of 1000 microns. After each five minute period the temperature of the oil sample is increased 20°C (6 steps from 40°C to 140°C).
The disc is then removed from the platen, and the wear scar caused by contact with the ball is measured (diameters X and Y) using an optical microscope provided with a calibrated graticule.
The results are shown below.
TABLE 7
Temperature (°C) Ref. Oil Ref. Oil + Adpack 0
40 0.12 0.099
60 0.126 0.111
80 0.133 0.115
100 0.133 0.115
120 0.134 0.116
140 0.135 0.119
Claims
1. A sulfur-containing boroester compound comprising: an acyclic thioalkyl borate ester having the general formula (I):
(OB)mR2
R'S(R4O)n-B (I)
\
(OB^R3
wherein R represents a hydrocarbyl radical having from 4 to 12 carbon atoms, R and R independently represent -(OR )nSR or -(OR )nSR OH; R represents a hydrocarbyl radical having from 1 to 6 carbon atoms; n is an integer of from 1 to 4; and 1 and m are independently 0, 1 or 2; or a thioalkyl-substituted cyclic metaborate ester having the general formula (II):
(II)
wherein n, R1 and R4, are defined as in formula (I); or a mixture of the acyclic thioalkyl borate ester of formula (I) and the thioalkyl- substituted cyclic metaborate ester of formula (II).
2. The sulfur-containing boroester compound as claimed in claim 1 wherein R represents a hydrocarbyl radical having from 6 to 9 carbon atoms; R represents a hydrocarbyl radical having from 2 to 4 carbon atoms; and 1, m and n are all 1.
3. The sulfur-containing boroester compound as claimed in either of the preceding claims wherein R represents a hydrocarbyl radical having 6 carbon atoms; and R represents a hydrocarbyl radical having 2 carbon atoms.
4. An oleaginous composition comprising, or made by admixing, a major amount of an oil of lubricating viscosity or of a power transmitting oil, and a minor amount of a sulfur-containing boroester compound as claimed in any of claims 1 to 3.
5. A method of making an oleaginous composition comprising blending a major amount of an oil of lubricating viscosity or of a power transmitting oil and a minor amount of a sulfur-containing boroester compound as claimed in any of claims 1 to 3.
6. The oleaginous composition or method as claimed in claims 4 or claim 5 wherein the sulfur-containing boroester compound comprises from between 0.001 to 5, such as 0.02 to 1, mass % of the composition.
7. The oleaginous composition or method as claimed in any of claims 4 to 6, wherein R represents a hydrocarbyl radical having from 6 to 9 carbon atoms; R represents a hydrocarbyl radical having from 2 to 4 carbon atoms; and 1, m and n are 1.
8. The oleaginous composition or method as claimed in claim 7 wherein R represents a hydrocarbyl radical having 6 carbon atoms; and R represents a hydrocarbyl radical having 2 carbon atoms.
9. The oleaginous composition or method as claimed in any of claims 4 to 8 wherein the oil is a synthetic oil or a natural oil.
10. The oleaginous composition or method as claimed in any of claims 4 to 9 further comprising one or more dispersants, viscosity modifiers, corrosion inhibitors, pour point depressants, anti-foaming agents, anti-wear agents, friction modifiers, detergents and rust inhibitors.
11. The oleaginous composition or method as claimed in claim 10 wherein the dispersant is a reaction product of polyisobutylene succinic anhydride and a hydrocarbyl polyamine.
12. An additive concentrate comprising a sulfur-containing boroester compound as claimed in any of claims 1 to 3 and an oleaginous carrier therefor.
13. A process for forming a sulfur-containing boroester compound which comprises reacting at least an equivalent molar amount of boric acid with an alkoxyalkyl sulfide.
14. The process as claimed in claim 13, wherein the said boric acid and alkoxyalkyl sulfide are reacted at a temperature within the range between 0 to 150, such as 60 to 120, ┬░C and at a pressure within the range of -100 to 0, such as -70 to -30, kPa.
15. The process as claimed in claim 13 or claim 14 wherein the boric acid and the alkoxyalkyl sulfide are reacted in the absence of a solvent.
16. The process as claimed in any of claims 13 to 15 wherein the alkoxyalkyl sulfide is hydroxyethyloctyl sulfide, hydroxyethyldodecyl sulfide, or l-hydroxy-2- methyl-3-thio-decane.
17. The process as claimed in any of claims 13 to 16 wherein the sulfur-containing boroeaster compound is as claimed in any of claims 1 to 3.
18. The product formed by the process as claimed in any of claims 13 to 17.
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US993619 | 1997-12-18 | ||
US08/993,619 US5885943A (en) | 1997-12-18 | 1997-12-18 | Sulfur boron antiwear agents for lubricating compositions |
PCT/EP1998/008125 WO1999032588A1 (en) | 1997-12-18 | 1998-12-14 | Antiwear agents for lubricating compositions |
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US (2) | US5885943A (en) |
EP (1) | EP0963428A1 (en) |
JP (1) | JP2002515918A (en) |
CN (1) | CN1103807C (en) |
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Families Citing this family (61)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5885943A (en) * | 1997-12-18 | 1999-03-23 | Exxon Chemical Patents Inc. | Sulfur boron antiwear agents for lubricating compositions |
JP4785315B2 (en) * | 2000-01-21 | 2011-10-05 | ユー.エス.ボラックス インコーポレイテッド | Nonaborate composition and production method thereof |
US6572847B2 (en) * | 2000-03-31 | 2003-06-03 | The Lubrizol Corporation | Elimination of odors from lubricants by use of a combination of thiazoles and odor masks |
JP2004521176A (en) * | 2001-02-07 | 2004-07-15 | ザ ルブリゾル コーポレイション | Lubricating oil composition |
US7197363B2 (en) | 2002-04-16 | 2007-03-27 | Vivant Medical, Inc. | Microwave antenna having a curved configuration |
US20050124510A1 (en) * | 2003-12-09 | 2005-06-09 | Costello Michael T. | Low sediment friction modifiers |
US7776035B2 (en) | 2004-10-08 | 2010-08-17 | Covidien Ag | Cool-tip combined electrode introducer |
US7282049B2 (en) | 2004-10-08 | 2007-10-16 | Sherwood Services Ag | Electrosurgical system employing multiple electrodes and method thereof |
US7553309B2 (en) | 2004-10-08 | 2009-06-30 | Covidien Ag | Electrosurgical system employing multiple electrodes and method thereof |
WO2006047360A2 (en) * | 2004-10-21 | 2006-05-04 | R.T. Vanderbilt Company, Inc. | Hydroxyalkyldithiocarbamate esters and borate esters |
JP5460310B2 (en) * | 2006-04-26 | 2014-04-02 | ヴァンダービルト ケミカルズ、エルエルシー | Antioxidant synergist for lubricating compositions |
US7846158B2 (en) | 2006-05-05 | 2010-12-07 | Covidien Ag | Apparatus and method for electrode thermosurgery |
CN101153237B (en) * | 2006-09-27 | 2012-07-25 | 吴桂琴 | Compound energy-saving antiwear agent of organic boron and method of producing the same |
US8211099B2 (en) | 2007-01-31 | 2012-07-03 | Tyco Healthcare Group Lp | Thermal feedback systems and methods of using the same |
US7998139B2 (en) | 2007-04-25 | 2011-08-16 | Vivant Medical, Inc. | Cooled helical antenna for microwave ablation |
US8181995B2 (en) | 2007-09-07 | 2012-05-22 | Tyco Healthcare Group Lp | Cool tip junction |
CN101418007B (en) * | 2007-10-25 | 2011-06-15 | 中国石油化工股份有限公司 | Compounds containing sulfur, boron and nitrogen and preparation method and use thereof |
US8435237B2 (en) | 2008-01-29 | 2013-05-07 | Covidien Lp | Polyp encapsulation system and method |
US8221418B2 (en) | 2008-02-07 | 2012-07-17 | Tyco Healthcare Group Lp | Endoscopic instrument for tissue identification |
US8192427B2 (en) | 2008-06-09 | 2012-06-05 | Tyco Healthcare Group Lp | Surface ablation process with electrode cooling methods |
US8251987B2 (en) | 2008-08-28 | 2012-08-28 | Vivant Medical, Inc. | Microwave antenna |
US8197473B2 (en) | 2009-02-20 | 2012-06-12 | Vivant Medical, Inc. | Leaky-wave antennas for medical applications |
US8246615B2 (en) | 2009-05-19 | 2012-08-21 | Vivant Medical, Inc. | Tissue impedance measurement using a secondary frequency |
US8292881B2 (en) | 2009-05-27 | 2012-10-23 | Vivant Medical, Inc. | Narrow gauge high strength choked wet tip microwave ablation antenna |
US8069553B2 (en) | 2009-09-09 | 2011-12-06 | Vivant Medical, Inc. | Method for constructing a dipole antenna |
US8355803B2 (en) | 2009-09-16 | 2013-01-15 | Vivant Medical, Inc. | Perfused core dielectrically loaded dipole microwave antenna probe |
US8394087B2 (en) | 2009-09-24 | 2013-03-12 | Vivant Medical, Inc. | Optical detection of interrupted fluid flow to ablation probe |
US8568398B2 (en) | 2009-09-29 | 2013-10-29 | Covidien Lp | Flow rate monitor for fluid cooled microwave ablation probe |
US9024237B2 (en) | 2009-09-29 | 2015-05-05 | Covidien Lp | Material fusing apparatus, system and method of use |
US8394092B2 (en) | 2009-11-17 | 2013-03-12 | Vivant Medical, Inc. | Electromagnetic energy delivery devices including an energy applicator array and electrosurgical systems including same |
US8491579B2 (en) | 2010-02-05 | 2013-07-23 | Covidien Lp | Electrosurgical devices with choke shorted to biological tissue |
US9561076B2 (en) | 2010-05-11 | 2017-02-07 | Covidien Lp | Electrosurgical devices with balun structure for air exposure of antenna radiating section and method of directing energy to tissue using same |
US9192436B2 (en) | 2010-05-25 | 2015-11-24 | Covidien Lp | Flow rate verification monitor for fluid-cooled microwave ablation probe |
US9241762B2 (en) | 2010-06-03 | 2016-01-26 | Covidien Lp | Specific absorption rate measurement and energy-delivery device characterization using image analysis |
US8672933B2 (en) | 2010-06-30 | 2014-03-18 | Covidien Lp | Microwave antenna having a reactively-loaded loop configuration |
US10588684B2 (en) | 2010-07-19 | 2020-03-17 | Covidien Lp | Hydraulic conductivity monitoring to initiate tissue division |
US9770294B2 (en) | 2011-01-05 | 2017-09-26 | Covidien Lp | Energy-delivery devices with flexible fluid-cooled shaft, inflow/outflow junctions suitable for use with same, and systems including same |
US10335230B2 (en) | 2011-03-09 | 2019-07-02 | Covidien Lp | Systems for thermal-feedback-controlled rate of fluid flow to fluid-cooled antenna assembly and methods of directing energy to tissue using same |
US9381059B2 (en) | 2011-04-05 | 2016-07-05 | Covidien Lp | Electrically-insulative hinge for electrosurgical jaw assembly, bipolar forceps including same, and methods of jaw-assembly alignment using fastened electrically-insulative hinge |
US9579150B2 (en) | 2011-04-08 | 2017-02-28 | Covidien Lp | Microwave ablation instrument with interchangeable antenna probe |
WO2012173671A1 (en) | 2011-06-17 | 2012-12-20 | Lubrigreen Biosynthetics, Llc | Compositions comprising estolide compounds and methods of making and using the same |
US8870860B2 (en) | 2011-08-09 | 2014-10-28 | Covidien Lp | Microwave antenna having a coaxial cable with an adjustable outer conductor configuration |
US9113930B2 (en) | 2012-01-05 | 2015-08-25 | Covidien Lp | Ablation systems, probes, and methods for reducing radiation from an ablation probe into the environment |
US9119648B2 (en) | 2012-01-06 | 2015-09-01 | Covidien Lp | System and method for treating tissue using an expandable antenna |
USD680220S1 (en) | 2012-01-12 | 2013-04-16 | Coviden IP | Slider handle for laparoscopic device |
US9364278B2 (en) | 2012-04-30 | 2016-06-14 | Covidien Lp | Limited reuse ablation needles and ablation devices for use therewith |
US8906008B2 (en) | 2012-05-22 | 2014-12-09 | Covidien Lp | Electrosurgical instrument |
US9901398B2 (en) | 2012-06-29 | 2018-02-27 | Covidien Lp | Microwave antenna probes |
US9993283B2 (en) | 2012-10-02 | 2018-06-12 | Covidien Lp | Selectively deformable ablation device |
US9522033B2 (en) | 2012-10-02 | 2016-12-20 | Covidien Lp | Devices and methods for optical detection of tissue contact |
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US9901399B2 (en) | 2012-12-17 | 2018-02-27 | Covidien Lp | Ablation probe with tissue sensing configuration |
WO2014160931A1 (en) | 2013-03-29 | 2014-10-02 | Covidien Lp | Step-down coaxial microwave ablation applicators and methods for manufacturing same |
CN105658164B (en) | 2013-09-06 | 2018-08-21 | 柯惠有限合伙公司 | microwave ablation catheter, handle and system |
US10631914B2 (en) | 2013-09-30 | 2020-04-28 | Covidien Lp | Bipolar electrosurgical instrument with movable electrode and related systems and methods |
US10624697B2 (en) | 2014-08-26 | 2020-04-21 | Covidien Lp | Microwave ablation system |
US10813691B2 (en) | 2014-10-01 | 2020-10-27 | Covidien Lp | Miniaturized microwave ablation assembly |
US10813692B2 (en) | 2016-02-29 | 2020-10-27 | Covidien Lp | 90-degree interlocking geometry for introducer for facilitating deployment of microwave radiating catheter |
EP3461877B1 (en) | 2017-09-27 | 2019-09-11 | Infineum International Limited | Improvements in and relating to lubricating compositions08877119.1 |
US11123094B2 (en) | 2017-12-13 | 2021-09-21 | Covidien Lp | Ultrasonic surgical instruments and methods for sealing and/or cutting tissue |
CN109680284B (en) * | 2019-02-28 | 2020-09-04 | 苏州纳孚林科金属表面技术有限公司 | Reductive borosulfate rust remover |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2346156A (en) * | 1942-02-16 | 1944-04-11 | Standard Oil Co | Compounded lubricant |
US2413718A (en) * | 1942-11-09 | 1947-01-07 | Continental Oil Co | Lubricant |
US2526506A (en) * | 1947-10-29 | 1950-10-17 | Standard Oil Dev Co | Hydrocarbon lubricant containing sulfurized aliphatic borates as stabilizers |
US3030196A (en) * | 1956-04-09 | 1962-04-17 | Ethyl Corp | Hydrocarbon fuels containing boron esters |
US3087936A (en) * | 1961-08-18 | 1963-04-30 | Lubrizol Corp | Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound |
US3303130A (en) * | 1965-11-02 | 1967-02-07 | Gulf Research Development Co | Lubricant compositions containing organo mercaptoalkyl borates |
FR1512479A (en) * | 1966-12-26 | 1968-02-09 | Piel Soc Ind Des Ets | Diving breathing helmet |
US3751367A (en) * | 1971-07-29 | 1973-08-07 | Monsanto Co | Compositions comprising boron compounds and polyphenyl thioethers |
GB1474048A (en) * | 1975-12-05 | 1977-05-18 | Exxon Research Engineering Co | Lubricating oil and fuel oil composiition |
US4031023A (en) * | 1976-02-19 | 1977-06-21 | The Lubrizol Corporation | Lubricating compositions and methods utilizing hydroxy thioethers |
US4394277A (en) * | 1981-10-26 | 1983-07-19 | Chevron Research Company | Method for improving fuel economy of internal combustion engines using borated sulfur-containing 1,2-alkane diols |
US4465605A (en) * | 1982-10-18 | 1984-08-14 | Mobil Oil Corporation | Borated polyhydroxyalkyl sulfides and lubricants containing same |
US4492640A (en) * | 1983-02-02 | 1985-01-08 | Mobil Oil Corporation | Trihydroxyhydrocarbyl sulfides and lubricants containing same |
EP0183642B1 (en) * | 1984-10-12 | 1989-03-08 | Ciba-Geigy Ag | Boron containing thioethers as additives |
EP0216909B1 (en) * | 1985-04-08 | 1990-02-28 | The Lubrizol Corporation | Lubricating oils comprising boron- and sulfur-containing compositions, and their method of preparation |
GB8707833D0 (en) * | 1987-04-02 | 1987-05-07 | Exxon Chemical Patents Inc | Sulphur-containing borate esters |
US4759873A (en) * | 1987-08-10 | 1988-07-26 | Mobil Company | Organic boron-sulfur compounds and lubricant compositions containing same |
US4857214A (en) * | 1988-09-16 | 1989-08-15 | Ethylk Petroleum Additives, Inc. | Oil-soluble phosphorus antiwear additives for lubricants |
CA2061141C (en) * | 1991-02-14 | 1996-09-10 | Makoto Nishio | Optical switching system for optical wavelength-division and time-division multiplexed signals |
WO1993011137A1 (en) * | 1991-12-06 | 1993-06-10 | The Lubrizol Corporation | Organophosphoryl borates and lubricants and aqueous fluids containing the same |
US5504240A (en) * | 1995-05-09 | 1996-04-02 | Aldrich Chemical Company, Inc. | Borane-hydroxydialkylsulfide borates |
US5885943A (en) * | 1997-12-18 | 1999-03-23 | Exxon Chemical Patents Inc. | Sulfur boron antiwear agents for lubricating compositions |
-
1997
- 1997-12-18 US US08/993,619 patent/US5885943A/en not_active Expired - Fee Related
-
1998
- 1998-11-25 US US09/200,343 patent/US6028210A/en not_active Expired - Fee Related
- 1998-12-14 WO PCT/EP1998/008125 patent/WO1999032588A1/en not_active Application Discontinuation
- 1998-12-14 CN CN98803628A patent/CN1103807C/en not_active Expired - Fee Related
- 1998-12-14 CA CA002281606A patent/CA2281606A1/en not_active Abandoned
- 1998-12-14 JP JP53327699A patent/JP2002515918A/en active Pending
- 1998-12-14 EP EP98964505A patent/EP0963428A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO9932588A1 * |
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CN1251125A (en) | 2000-04-19 |
CA2281606A1 (en) | 1999-07-01 |
US5885943A (en) | 1999-03-23 |
CN1103807C (en) | 2003-03-26 |
US6028210A (en) | 2000-02-22 |
WO1999032588A8 (en) | 1999-08-26 |
JP2002515918A (en) | 2002-05-28 |
WO1999032588A1 (en) | 1999-07-01 |
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